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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 33, Number 12
BKCSDE 33(12)
December 20, 2012 

 
Title
Rate and Product Studies on the Solvolyses of Allyl Chloroformate
Author
Han Joong Koh*, Suk Jin Kang
Keywords
Allyl chloroformate, Extended grunwald-winstein equation, SN2 mechanism, Solvent kinetic isotope effect, Product selectivity
Abstract
The solvolysis rate constants of allyl chloroformate (CH2=CHCH2OCOCl, 3) in 30 different solvents are well correlated with the extended Grunwald-Winstein equation, using the NT solvent nucleophilicity scale and YCl solvent ionizing scale, with the sensitivity values of 0.93 ± 0.05 and 0.41 ± 0.02 for l and m, respectively. These l and m values can be considered to support a SN2 reaction pathway. The activation enthalpies (ΔH≠) were 12.5 to 13.4 kcal·mol−1 and the activation entropies (ΔS≠) were −34.4 to −37.3 cal·mol−1·K−1, which is also consistent with the proposed bimolecular reaction mechanism. The solvent kinetic isotope effect (SKIE, kMeOH/kMeOD) of 2.16 was also in accord with the SN2 mechanism. The values of product selectivity (S) for the solvolyses of 3 in alcohol/water mixtures was 1.3 to 3.9, which is also consistent with the proposed bimolecular reaction mechanism.
Page
4117 - 4121
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